WO2004009697A1 - ポリオレフィン樹脂組成物 - Google Patents
ポリオレフィン樹脂組成物 Download PDFInfo
- Publication number
- WO2004009697A1 WO2004009697A1 PCT/JP2003/009071 JP0309071W WO2004009697A1 WO 2004009697 A1 WO2004009697 A1 WO 2004009697A1 JP 0309071 W JP0309071 W JP 0309071W WO 2004009697 A1 WO2004009697 A1 WO 2004009697A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyolefin resin
- modified
- resin composition
- layered silicate
- infrared absorption
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Definitions
- the present invention relates to a polyolefin resin composition having excellent heat resistance and flame retardancy, and a method for producing the same.
- Polyolefin resins typified by polyethylene, polypropylene, etc. are used in various applications, such as packaging materials, automotive materials, and home appliance materials.
- inorganic substances such as talc and glass fiber as a filler
- the inorganic filler is agglomerated on the order of micrometers in the resin, so that a considerable amount of inorganic filler is required to obtain a sufficient effect, and a weight reduction is required. There is a problem that it is not suitable for the intended use.
- the layered silicate is dispersed in the resin on a nano-order. Therefore, it is reported that the elastic modulus and heat resistance of the resin can be improved with a relatively small amount of addition.
- this method is limited to polar polymers that have a high affinity for layered silicates, and cannot be applied to polyolefins such as polyethylene and polypropylene.
- Japanese Patent Application Laid-Open No. H10-30939 discloses a monomer having a product of an unsaturated carboxylic acid or a derivative thereof and a reactivity ratio thereof of 1 or less.
- Modified polyolefin resin obtained by block or graft copolymerization of styrene, etc. and a modified layered silicate are melted
- a method of kneading is disclosed. According to this method, it is reported that the layered silicate as a filler can be uniformly dispersed in a polyolefin resin, and it is reported that the polyolefin composite material obtained by this method has excellent elastic modulus and heat resistance. .
- Japanese Patent Application Laid-Open No. 10-188292 discloses a polyolefin resin matrix by using a layered gayate intercalated with a functional group-containing polyolefin oligomer.
- a method for dispersing layered clay minerals well is disclosed. Specifically, a specific amount of maleic acid-modified polyolefin oligomer is added in order to highly disperse the layered silicate in polypropylene.
- the disclosed method can be applied to polypropylene, even if a similar technique is used for polyethylene resins such as high-density polyethylene (HDPE) and low-density polyethylene (LDPE), the layered silicate can be highly dispersed. It has been clarified by the inventor's research that this is not possible.
- HDPE high-density polyethylene
- LDPE low-density polyethylene
- the modified polyolefin resin of the polyolefin resin composition containing the modified lamellar silicate, the modified polyolefin resin and the polyolefin resin is a carboxylic acid-modified polyolefin satisfying a specific condition, any of the polyolefin resins including polyethylene
- a modified layered silicate obtained by treating a surfactant with a surfactant can be uniformly dispersed in a polyolefin resin, and the polyolefin resin composition of the present invention thus obtained is an original polyolefin resin.
- the inventors have found that heat resistance and flame retardancy are improved without losing the properties of the resin such as hydrophobicity, and have completed the present invention.
- the present invention is as follows.
- a polyolefin resin composition containing a modified lamellar silicate, a modified polyolefin resin, and a polyolefin resin, wherein the modified polyolefin resin is a carboxylic acid obtained from an infrared absorption spectrum using the formula (1).
- the degree of modification (P el) is from 0.030 to 0.100, and the degree of hydrogen-bonding carboxyl modification (P c H) obtained using equation (2) is 0.80 or more.
- a polyolefin resin composition characterized in that: -
- I CO l Infrared absorption intensity of the peak existing at 1780 to 1790 cm— 1
- ICO 2 Infrared absorption intensity of the peak existing at 1170 to 1720 cm— 1 3: IC 01 + IC 02
- the mass composition ratio of the modified layered silicate, the modified polyolefin resin, and the polyolefin resin is 0.01 to 40%.
- polyolefin resin composition according to any one of 1 to 3, wherein the polyolefin resin is a polyethylene resin.
- Fig. 2 is an enlarged view of the infrared absorption spectrum of Fig. 1 from 160 cm- 1 to 1900 cm-11.
- FIG. 3 is an infrared absorption spectrum of the modified polyolefin resin used in Comparative Example 4.
- Fig. 4 is an enlarged view of the infrared absorption spectrum of FIG. 3 at 160 cm- 1 to 190 cm- 1 .
- FIG. 5 is a graph showing the X-ray diffraction patterns of the polyolefin resin composition films obtained in Example 1, Comparative Example 1, and Comparative Example 4 of the present invention.
- the modified layered silicate used in the present invention is obtained by modifying the layered silicate.
- Layered silicates are 2: 1 type clay minerals, such as talc, pyrophyllite, smectite, palmikilite, and myriki. These may be any of those obtained by refining natural minerals, those obtained by hydrothermal synthesis, melt synthesis, and calcination synthesis. Among them, smectite and my strength, particularly fluorinated synthetic my strength, are preferable. In the case of smectites, the types include naturally occurring montmorillonite and paiderite, synthetic hectite, and synthetic saponite.
- the modification in the modified layered silicate is not limited as long as the layered silicate serving as a host and another compound are chemically bonded, ion-bonded, hydrogen-bonded, or the like.
- Compounds for the intercalation method are not limited, for example, long-chain alcohol, A carboxylic acid, a surfactant, a silane coupling agent and the like are used, and among them, a surfactant is preferable.
- Anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants. Preferred are cationic and nonionic surfactants.
- cationic surfactants include quaternary ammonium salts such as dodecyltrimethylammonium bromide or dodecyltrimethylammonium chloride, octane decyltrimethylammonium bromide, and octadecyltrimethylammonium. Amines such as min;
- hydrophilic portion of the nonionic surfactant examples include ethylene oxide (EO), propylene oxide (Po), or a copolymer thereof, and a hydroxyl group.
- hydrophobic portion examples include a long-chain saturated or unsaturated alkyl group.
- specific examples of nonionic surfactants include, for example, ethers of polyethylene glycol such as polyethylene glycol stearyl ether and polyethylene daricol lauryl ether, and polyethylene glycol perstearate and polyethylene daricol laurate. Examples include carboxylic acid esters of polyethylene glycol.
- a modification means a method of three-dimensionally cross-linking the layered silicates by a method in which a silanol group at the terminal of the layered silicate is subjected to a power-supplying agent treatment or the like can also be mentioned.
- the interlayer distance (h 0) of the modified layered silicate as a raw material is preferably set to a specific value. Preferably, it is greater than approximately 5.83 angstroms and less than 20.0 angstroms. More preferably, it is greater than 8.9 ⁇ and less than 15.5 ⁇ .
- the value of h 0 can be obtained from the following equation by X-ray diffraction.
- h O can be controlled by the denaturant of the layered silicate, for example, in the case of a surfactant, by the chain length of the hydrophobe thereof. The longer the chain length, the larger h 0.
- h 0 can also be changed by a head group (primary, secondary or tertiary) of an ammonium salt.
- h0 can be controlled by using layered silicates having different ion exchange amounts (chargexcchangeccap: CEC).
- the aspect ratio (layer length / layer thickness) of the microcrystals of the lamellar silicate is 5%. It is preferably at least 000, more preferably at least 300.
- the aspect ratio of the layered silicate can be determined by scanning electron microscope (SEM) 'or transmission electron microscope (TEM) measurements.
- the modified polyolefin resin used in the present invention means a polyolefin resin obtained by chemically modifying a main chain and side chains.
- the chemical modification may be at least modified with a modifying group having a carbonyl group, and may contain a functional group such as a hydroxyl group, a nitro group, or an imido group in addition to the carbonyl group. And it is preferable that the modifying group is present at the terminal of the molecule of the polyolefin resin. Polyolefin resins having a modifying group at both ends are also preferably used. If the structure of the polyolefin resin is branched, there may be three or more terminals. In this case, the modifying group may be basically contained at any terminal, but it is preferable that the modifying group is present at the terminal of the main chain. Further, those having a modifying group at a plurality of terminals and polyolefin resins containing a plurality of different types of modifying groups are also preferably used.
- the method for producing the modified polyolefin resin is not particularly limited, and examples thereof include a polymerization type in which the polyolefin resin is polymerized and then modified, or a method in which the polyolefin resin is modified when decomposing the high-molecular-weight polyolefin resin, with the polymerization method being preferred.
- the polyolefin resin used in the modified polyolefin resin of the present invention includes, for example, a homopolymer of 0! Olefin such as ethylene, propylene, butene-1, hexene-1, or a mixture of two or more of these.
- random or block copolymers such as polyethylene, polypropylene, polybutene-1, polyisobutene, and ethylene-propylene copolymer.
- cyclic polyolefins represented by Abel (trademark) manufactured by Mitsui Chemicals, Inc. and Zeonex (trademark) manufactured by Zeon Corporation are also preferably used.
- polyethylene resins examples include high-pressure low-density polyethylene (LDPE), linear low- and medium-density polyethylene (MDPE) obtained by copolymerizing ethylene with a-olefin, ethylene-a-olefin-copolymerized plastomer or elastomer, and high-density polyethylene.
- LDPE high-pressure low-density polyethylene
- MDPE linear low- and medium-density polyethylene
- HDPE high-density polyethylene
- EPDM ethylene propylene-gen rubber
- the molecular weight of the modified polyolefin resin is not limited, but is preferably 100 or more in terms of weight average molecular weight (Mw) from the viewpoint of compatibility with the polyolefin resin.
- the degree of carboxylic acid modification of the modified polyolefin resin must be in the range of Pc 1 force SO 0.030 to 0.10. Is preferred. Particularly preferably, it is in the range of 0.040 to 0.060.
- Pel is lower than 0.030; the physical properties of the obtained polyolefin resin composition are not improved because the overall degree of carboxylic acid modification is low. Properties larger than 0.10 0 do not improve their properties.
- the degree of carboxylic acid modification (Pel) and the degree of hydrogen-bonding carboxyl modification (PcH) of the modified polyolefin resin of the present invention can be determined by infrared absorption spectrometry.
- the degree of carboxylic acid modification (P e1) and the degree of hydrogen bonding lipoxyl modification (P c H) are defined by the following equations (1) and (2).
- IC 01 1 7 8 0 ⁇ 1 7 9 0 cm- 1 exists in the peak of the infrared absorption intensity
- IC 02 1 7 1 0 ⁇ 1 7 2 0 cm- 1 infrared absorption intensity of the peaks present in IC_ ⁇ 3: IC 0 1 + IC 02
- ICH 2 is the infrared absorption intensity of the peak attributed to the asymmetric stretching vibration of the methylene group, which corresponds to the main skeleton of the modified polyolefin resin, and is found in all polyolefin resins. In some cases, it is the peak top is (2 9 2 0 ⁇ 3) cm 1, if so, the infrared absorption intensity of the peak and I CH 2.
- both ICO 1 and IC 02 are the infrared absorption intensities of the peaks attributed to the stretching vibration of the force luponyl, and IC 01 is derived from the carbonyl of carboxylic anhydride formed by dehydration condensation polymerization of carboxylic acids.
- ICO 2 is the infrared absorption intensity of the carbonyl peak derived from carboxylic acid.
- I C03 is the sum of I C O I and I C 02.
- a solid sample of the modified polyolefin resin is ground, and the flakes are directly subjected to infrared absorption measurement by a transmission method. Do not use molding methods. This is because the degree of modification of the modified polyolefin resin may change during the dissolving and drying processes.
- FIG. 1 is a chart of an infrared absorption spectrum of the modified polyolefin resin of Example 1.
- the peak corresponding to the IC H 2 shown in FIG. Fig2 is in the infrared absorption scan Bae-vector charts Figl, larger 1 6 0 0 cm- 1 ⁇ 1 9 0 0 cm one 1 near the scan Bae-vector absorption corresponding to Karuponiru group and Me certification It is displayed.
- the peaks corresponding to IC 01 and ICO 2 are shown in the figure.
- FIG. 3 is a chart of an infrared absorption spectrum of the modified polyolefin resin of Comparative Example 4.
- Fig. 4 is an enlarged view of the chart of Fig. 3 around 160 cm- 1 to 1900 cm_1.
- P c 1 and P c H are obtained in the same manner as in FIGS. 1 and 2, P el becomes 0.101 and P c H becomes 0.49.
- the modified polyolefin resin that can be used in the present invention is described above.
- the polyolefin resin used in the polyolefin resin composition of the present invention together with the modified polyolefin resin may be the same polyolefin resin as the polyolefin resin used in the modified polyolefin resin.
- the polyolefin resin may be the same or different from the polyolefin resin used for the modified polyolefin resin.
- modified layered silicate, the modified polyolefin resin, and the polyolefin resin constituting the polyolefin resin composition of the present invention have been described above.
- the modified layered silicate contributes to the improvement of the heat resistance and the flame retardancy of the polyolefin resin composition, if the ratio of the modified layered silicate is too large, the melt viscosity increases and the processability is reduced. descend. Therefore, the mass composition ratio of the modified lamellar silicate, the modified polyolefin resin, and the polyolefin resin (modified lamellar silicate z modified polyolefin resin z polyolefin resin) is from 0.
- the polyolefin resin composition of the present invention contains additives such as antioxidants, anti-blocking agents, heat stabilizers, ultraviolet absorbers, flame retardants, dyes, pigments, and plasticizers that are usually used in the art. Can be added. If necessary, inorganic or organic reinforcing agents can be added. It is also possible to blend resin other than polyolefin resin.
- a method for producing the polyolefin resin composition of the present invention will be described.
- a method for mixing the modified lamellar silicate, the modified polyolefin resin, and the polyolefin resin a method used in the art can be used.
- mixing and dispersing may be performed by a commonly used method such as a kneader such as a Pampari mixer or a roll mixer or a twin-screw extruder.
- a kneader such as a Pampari mixer or a roll mixer or a twin-screw extruder.
- the order of addition of each component should be as follows. preferable.
- the polyolefin resin composition of the present invention obtained as described above is excellent in heat resistance and flame retardancy because the modified lamellar silicate is uniformly dispersed, but the dispersibility in the present invention is as follows. Evaluate by method.
- whether or not the modified layered silicate has high dispersibility is estimated from the interlayer distance (h) of the modified layered silicate obtained by X-ray diffraction.
- 9.5 angstroms is the thickness of one layer of the modified layered silicate, and the value hardly changes with any modified layered silicate.
- d can be calculated by X-ray diffraction measurement from the peak position (2 ⁇ ) corresponding to the bottom surface reflection of the plane 01 of the modified layered keic acid using the following Bragg equation.
- Fig. 5 is modified layered silicates in the polyolefin resin compositions of Example 1, Comparative Example 1, and Comparative Example 4, respectively, and d in Fig. 5 is a modified layered silicate as a raw material. It is an X-ray diffraction pattern of (N an omer 1.3 OP).
- the peak position of the modified layered silicate does not change at all, the physical properties hardly improve because the modified layered silicate is not dispersed at all.
- a polyolefin resin composition in which h is 65 ⁇ or more has excellent heat resistance and flame retardancy, and more preferably h is 75 ⁇ or more.
- the polyolefin resin composition of the present invention has been described above.
- the polyolefin resin composition of the present invention can be formed into a film by extrusion molding such as water-cooled or air-cooled inflation molding, extrusion molding using a T-die, and extrusion lamination molding.
- the polyolefin resin composition of the present invention can be formed into a wrap film obtained by further extending the above film.
- it can be used for injection molding, professional molded products, foamed products such as bead foaming, extrusion foaming, and sheet products produced by pod molding.
- foamed products such as bead foaming, extrusion foaming, and sheet products produced by pod molding.
- the measuring method used in the present invention is as follows.
- a film (2 mm thickness) of the polyolefin resin composition is measured using an X-ray diffractometer RINT 2000 (trademark) manufactured by Rigaku Corporation using Cu ⁇ ray. Other measurement conditions are as shown below.
- Accelerating voltage 40 kV, accelerating current: 200 mA, scanning speed: 2 ° / min, divergence, scattering slit 1 ° 6 °, receiving slit width: 0.15 mm
- a microscope IR measuring device of IR ⁇ s manufactured by Spectra Techh Co., Ltd. is used.
- the pellet of the modified polyolefin resin is crushed, and the flake is measured by a transmission method.
- the measurement conditions are as shown below.
- Test pieces (100 mm long x 3 mm thick) in accordance with AS TM (America Materials Testing Association) E 1 3 5 4 (Building Materials Combustion Testing Method), 50 kW by corn calorime / irradiating the heat of m 2, referred to as the maximum heat release rate (H eat R elease R ate after HRR, a quantity representing the amount of heat generated during combustion, combustion smaller the value is suppressed, is flame retardant Is used as an index of flame retardancy.
- H eat R elease R ate after HRR a quantity representing the amount of heat generated during combustion, combustion smaller the value is suppressed
- the heat transfer medium is heated at a constant speed while applying the specified bending stress to the test piece in the heating bath, and the test piece has the specified deflection. Is reached, and the temperature of the heat transfer medium at the time of the heat transfer is defined as the heat distortion temperature.
- the evaluation is ⁇ , if it is 85 ° C or more and less than 90, ⁇ is evaluated, and if it is less than 85, X is evaluated.
- Example 1 30 g of organically modified montmorillonite Nanomerl.30P (trademark) manufactured by Nantec Corporation as a modified layered silicate, and high-density resin manufactured by Nii Chemicals Co., Ltd. as a modified polyolefin resin.
- wax 2203A trademark
- Lapoplast mill MR50 type trademark
- 80 g of a high-density polyethylene resin S360 manufactured by Asahi Kasei Corporation was added as a polyolefin resin, and the mixture was kneaded for 10 minutes to obtain a polyolefin resin composition.
- the mixing conditions are as follows. Rotation speed: 50 rpm, temperature: 180.
- the obtained composition was press-pressed at 180 ° C. and quenched, and then stretched 3 ⁇ 3 times by a batch-type biaxial stretching apparatus at 80 ° C. to obtain a film having a thickness of about 30 im. .
- Table 1 shows the results of evaluating the HRR and heat distortion temperature using this film.
- the infrared absorption spectrum of the modified polyolefin resin used in this example is shown in FIGS.
- the X-ray diffraction pattern of the obtained polyolefin resin composition film is shown in Fig. 5a, and the X-ray diffraction pattern of the modified layered silicate as a raw material is shown in Fig. 5d.
- Table 1 shows the results of evaluating the HRR and heat distortion temperature of the obtained film of the polyolefin resin composition.
- a cationic surfactant 4 g of octadecyltrimethylammonium bromide (manufactured by A1drich Co., Ltd.) was dissolved in 200 g of ethanol (referred to as solution A).
- solution A ethanol
- a homomixer for 300 g Dispersed referred to as liquid B. After mixing Solution A and Solution B, the mixture was stirred at 50 for 24 hours.
- This polyolefin resin composition was formed into a film under the same conditions as in Example 1 to obtain a polyolefin resin composition film.
- Table 1 shows the results of evaluating the HRR and heat distortion temperature of this film.
- Example was obtained using 4 g of the modified modified layered silicate and modified polyolefin resin.
- 80 g of high-density polyethylene resin S360 manufactured by Asahi Kasei Corporation was mixed in the same manner as in Example 1 with 16 g of high wax 222 A used as in 1 as polyolefin resin. .
- a film of a polyolefin resin composition having a thickness of 30 ⁇ m and a width of 30 cm was prepared using a T-die type film extruder (manufactured by Toyo Seiki Co., Ltd.).
- Example 1 A film was produced in the same manner as in Example 1 by using 4 g of the modified layered silicate Nanomerl.
- Table 1 shows the results of evaluating the HRR and heat distortion temperature of the obtained film.
- the X-ray diffraction pattern of the obtained film is shown in Fig. 5b.
- a film was produced under the same conditions except that the modified layered silicate used in Example 1 was not used.
- Table 1 shows the results of evaluating the HRR and heat distortion temperature of this film.
- polyolefin resin composition of the present invention By using the polyolefin resin composition of the present invention, a polyolefin resin molded article having high heat resistance and high flame retardancy can be obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03741446A EP1553136B1 (en) | 2002-07-19 | 2003-07-17 | Polyolefin resin composition |
US10/517,828 US20050239941A1 (en) | 2002-07-19 | 2003-07-17 | Polyolefin resin composition |
AU2003281617A AU2003281617A1 (en) | 2002-07-19 | 2003-07-17 | Polyolefin resin composition |
JP2004522743A JPWO2004009697A1 (ja) | 2002-07-19 | 2003-07-17 | ポリオレフィン樹脂組成物 |
KR1020047020832A KR100619642B1 (ko) | 2002-07-19 | 2003-07-17 | 폴리올레핀 수지 조성물 |
DE60311500T DE60311500T2 (de) | 2002-07-19 | 2003-07-17 | Polyolefinharzzusammensetzung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-210604 | 2002-07-19 | ||
JP2002210604 | 2002-07-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004009697A1 true WO2004009697A1 (ja) | 2004-01-29 |
Family
ID=30767740
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/009071 WO2004009697A1 (ja) | 2002-07-19 | 2003-07-17 | ポリオレフィン樹脂組成物 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20050239941A1 (ja) |
EP (1) | EP1553136B1 (ja) |
JP (1) | JPWO2004009697A1 (ja) |
KR (1) | KR100619642B1 (ja) |
CN (1) | CN1307251C (ja) |
AT (1) | ATE352582T1 (ja) |
AU (1) | AU2003281617A1 (ja) |
DE (1) | DE60311500T2 (ja) |
WO (1) | WO2004009697A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007049734A1 (ja) * | 2005-10-28 | 2007-05-03 | Asahi Kasei Chemicals Corporation | ポリエチレン系樹脂組成物及びそのフィルム |
CN1326931C (zh) * | 2004-12-12 | 2007-07-18 | 青岛大学 | 聚烯烃/层状硅酸盐纳米复合物的制备方法 |
CN100410309C (zh) * | 2005-02-21 | 2008-08-13 | 中国科学院化学研究所 | 聚烯烃/蒙脱土纳米复合材料的制备方法 |
JP2009209267A (ja) * | 2008-03-04 | 2009-09-17 | Japan Polyethylene Corp | ポリエチレン系容器蓋 |
US12104048B2 (en) | 2018-03-29 | 2024-10-01 | Agency For Science, Technology And Research | Reinforced polyolefin composite |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7648771B2 (en) * | 2003-12-31 | 2010-01-19 | Kimberly-Clark Worldwide, Inc. | Thermal stabilization and processing behavior of block copolymer compositions by blending, applications thereof, and methods of making same |
CN101023132B (zh) * | 2004-09-16 | 2010-06-02 | 旭化成化学株式会社 | 耐热性优异的脂肪族聚酯树脂组合物 |
US8377027B2 (en) | 2005-04-29 | 2013-02-19 | Kimberly-Clark Worldwide, Inc. | Waist elastic members for use in absorbent articles |
US8751169B1 (en) * | 2010-09-29 | 2014-06-10 | The United States of America, as represented by the Secretary of the Department of the Interior | Spectral method for determining the source of expanded vermiculite insulation in attics and walls |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10130434A (ja) * | 1996-11-01 | 1998-05-19 | Du Pont Kk | 低密度ポリエチレン−層状珪酸塩複合材料およびその製造方法 |
WO2000061676A1 (fr) * | 1999-04-12 | 2000-10-19 | Sekisui Chemical Co., Ltd. | Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique |
JP2002030181A (ja) * | 2000-07-14 | 2002-01-31 | Jsp Corp | 発泡用ポリオレフィン系樹脂組成物 |
JP2002037940A (ja) * | 2000-07-21 | 2002-02-06 | Grand Polymer Co Ltd | ポリプロピレン樹脂組成物および製造方法 |
JP2002060555A (ja) * | 2000-08-11 | 2002-02-26 | Sekisui Chem Co Ltd | ポリオレフィン系複合材料及びその製造方法 |
JP2003003027A (ja) * | 2001-06-19 | 2003-01-08 | Idemitsu Petrochem Co Ltd | ポリプロピレン系複合樹脂組成物 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5869025A (ja) * | 1981-10-21 | 1983-04-25 | Toyo Ink Mfg Co Ltd | 塗装可能な未変性ポリオレフイン系樹脂成型物の製造方法 |
EP0747322B1 (en) * | 1995-06-05 | 2001-09-12 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite clay material and method for producing the same, blend material and composite clay rubber using the same and production method thereof |
JPH09302170A (ja) * | 1996-05-14 | 1997-11-25 | Mitsui Petrochem Ind Ltd | 変性ポリエチレン樹脂組成物、易リサイクル性樹脂組成物、多層積層体および容器 |
JP2001064454A (ja) * | 1999-08-30 | 2001-03-13 | Sekisui Chem Co Ltd | ポリオレフィン系樹脂複合材料 |
JP2001026724A (ja) * | 1999-07-16 | 2001-01-30 | Sekisui Chem Co Ltd | 熱可塑性樹脂複合材料及びその製造方法 |
JP2000355640A (ja) * | 1999-04-12 | 2000-12-26 | Sekisui Chem Co Ltd | ポリオレフィン系複合材料 |
JP2001181513A (ja) * | 1999-12-24 | 2001-07-03 | Konica Corp | 複合材料の製造方法、複合材料及び成形品 |
US6632868B2 (en) * | 2000-03-01 | 2003-10-14 | Amcol International Corporation | Intercalates formed with polypropylene/maleic anhydride-modified polypropylene intercalants |
JP4356212B2 (ja) * | 2000-08-09 | 2009-11-04 | コニカミノルタビジネステクノロジーズ株式会社 | 静電荷像現像用トナー |
JP2002192663A (ja) * | 2000-12-22 | 2002-07-10 | Polyplastics Co | 熱溶着用シート、それを用いた複合成形品並びにその製造法 |
US6841226B2 (en) * | 2001-11-13 | 2005-01-11 | Eastman Kodak Company | Ethoxylated alcohol intercalated smectite materials and method |
US6844389B2 (en) * | 2001-12-20 | 2005-01-18 | Equistar Chemicals, Lp | Ethylene polymer compositions having improved melt strength |
-
2003
- 2003-07-17 KR KR1020047020832A patent/KR100619642B1/ko not_active IP Right Cessation
- 2003-07-17 WO PCT/JP2003/009071 patent/WO2004009697A1/ja active IP Right Grant
- 2003-07-17 US US10/517,828 patent/US20050239941A1/en not_active Abandoned
- 2003-07-17 JP JP2004522743A patent/JPWO2004009697A1/ja active Pending
- 2003-07-17 AT AT03741446T patent/ATE352582T1/de not_active IP Right Cessation
- 2003-07-17 EP EP03741446A patent/EP1553136B1/en not_active Expired - Lifetime
- 2003-07-17 CN CNB038163721A patent/CN1307251C/zh not_active Expired - Fee Related
- 2003-07-17 AU AU2003281617A patent/AU2003281617A1/en not_active Abandoned
- 2003-07-17 DE DE60311500T patent/DE60311500T2/de not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10130434A (ja) * | 1996-11-01 | 1998-05-19 | Du Pont Kk | 低密度ポリエチレン−層状珪酸塩複合材料およびその製造方法 |
WO2000061676A1 (fr) * | 1999-04-12 | 2000-10-19 | Sekisui Chemical Co., Ltd. | Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique |
JP2002030181A (ja) * | 2000-07-14 | 2002-01-31 | Jsp Corp | 発泡用ポリオレフィン系樹脂組成物 |
JP2002037940A (ja) * | 2000-07-21 | 2002-02-06 | Grand Polymer Co Ltd | ポリプロピレン樹脂組成物および製造方法 |
JP2002060555A (ja) * | 2000-08-11 | 2002-02-26 | Sekisui Chem Co Ltd | ポリオレフィン系複合材料及びその製造方法 |
JP2003003027A (ja) * | 2001-06-19 | 2003-01-08 | Idemitsu Petrochem Co Ltd | ポリプロピレン系複合樹脂組成物 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1326931C (zh) * | 2004-12-12 | 2007-07-18 | 青岛大学 | 聚烯烃/层状硅酸盐纳米复合物的制备方法 |
CN100410309C (zh) * | 2005-02-21 | 2008-08-13 | 中国科学院化学研究所 | 聚烯烃/蒙脱土纳米复合材料的制备方法 |
WO2007049734A1 (ja) * | 2005-10-28 | 2007-05-03 | Asahi Kasei Chemicals Corporation | ポリエチレン系樹脂組成物及びそのフィルム |
JP2009209267A (ja) * | 2008-03-04 | 2009-09-17 | Japan Polyethylene Corp | ポリエチレン系容器蓋 |
US12104048B2 (en) | 2018-03-29 | 2024-10-01 | Agency For Science, Technology And Research | Reinforced polyolefin composite |
Also Published As
Publication number | Publication date |
---|---|
EP1553136A4 (en) | 2006-03-15 |
US20050239941A1 (en) | 2005-10-27 |
ATE352582T1 (de) | 2007-02-15 |
JPWO2004009697A1 (ja) | 2005-11-17 |
KR20050010962A (ko) | 2005-01-28 |
DE60311500D1 (de) | 2007-03-15 |
EP1553136B1 (en) | 2007-01-24 |
KR100619642B1 (ko) | 2006-09-08 |
DE60311500T2 (de) | 2007-11-08 |
CN1307251C (zh) | 2007-03-28 |
AU2003281617A1 (en) | 2004-02-09 |
EP1553136A1 (en) | 2005-07-13 |
CN1668687A (zh) | 2005-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6271297B1 (en) | General approach to nanocomposite preparation | |
Yuan et al. | Efficient grafting of polypropylene onto silica nanoparticles and the properties of PP/PP-g-SiO2 nanocomposites | |
TWI257404B (en) | Polyolefin-based nanocomposite and preparation thereof | |
EP1487912A1 (en) | Cross-linkable and/or cross-linked nanofiller compositions | |
Azizi et al. | Effect of layered silicate nanoclay on the properties of silane crosslinked linear low-density polyethylene (LLDPE) | |
Razmjooei et al. | Preparation of dynamically vulcanized thermoplastic elastomer nanocomposites based on LLDPE/reclaimed rubber | |
WO2004009697A1 (ja) | ポリオレフィン樹脂組成物 | |
Chowdhury et al. | Molecular-scale design of a high performance organic–inorganic hybrid with the help of gamma radiation | |
KR20020002786A (ko) | 폴리프로필렌-유기점토 복합체 및 이의 제조방법 | |
KR100872859B1 (ko) | 고함량 나노클레이 마스터배치 제조 및 이를 이용한 고강성폴리프로필렌/나노클레이 복합재 제조 | |
KR100371232B1 (ko) | 난연성이 우수한 폴리프로필렌-유기점토 복합체 및 이의제조방법 | |
WO2004033549A1 (en) | Polymer composition comprising nanofillers | |
Liao et al. | Preparation of Poly (ethylene‐octene) Elastomer/Clay/Wood Flour Nanocomposites by a Melting Method | |
KR100529365B1 (ko) | 폴리프로필렌-층상구조점토 나노복합체 조성물 및 그의제조방법 | |
TWI290156B (en) | Method for preparation of polyolefin nanocomposite | |
Kuila et al. | Polyolefin-based polymer nanocomposites | |
JP2002167484A (ja) | ポリプロピレン系樹脂組成物およびその製造方法 | |
JP2000281841A (ja) | 層状珪酸塩複合材料、その製造方法および該複合材料からなる成形体 | |
Li et al. | Microstructure and properties of poly (butylene terephthalate) based nanocomposites | |
CN111836856B (zh) | 橡胶共混物、其制品和其制造方法 | |
JP2009062520A (ja) | ポリエチレン系成形材料及びその成形体 | |
KR20050112144A (ko) | 클레이를 이용하여 기계적 물성 및 난연성이 향상된폴리프로필렌계 수지 조성물 및 이를 이용한 전선 | |
Merchan Sandoval et al. | Polypropylene nanocomposites produced by in situ grafting of n‐butyl acrylate | |
Merchán Sandoval et al. | Polypropylene nanocomposites produced by in‐situ grafting of maleic anhydride using different mixing procedures | |
Namvar Maroofy et al. | Ionic Cross-Linking of Polypropylene: Effect of Maleic Anhydride Grafting Temperature and Ionic Plasticizer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004522743 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003741446 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10517828 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020047020832 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20038163721 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 1020047020832 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003741446 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 2003741446 Country of ref document: EP |